CN113264538B - Preparation method and application of molecular sieve adsorbent based on LiNaKLSX - Google Patents
Preparation method and application of molecular sieve adsorbent based on LiNaKLSX Download PDFInfo
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- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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Abstract
The invention relates to a preparation method and application of a molecular sieve adsorbent based on LiNaKLSX, belonging to the technical field of adsorbents; the technical problem to be solved is to synthesize and prepare a molecular sieve adsorbent which can be used in the field of PSA/VPSA air separation oxygen generation and has higher oxygen production; the technical scheme is as follows: the method comprises the following steps: the method comprises the following steps: preparing a lithium sodium potassium type low-silicon X type molecular sieve LiNaKLSX molecular sieve, and performing the second step: exchanging the LiNaKLSX molecular sieve into a LiLSX molecular sieve through Li +, and performing the third step: mixing the prepared LiLSX molecular sieve powder with clay, adding an auxiliary agent, forming by a ball forming mill or a strip extruding machine, drying and roasting to obtain a molecular sieve adsorbent; the invention can effectively reduce the preparation cost, has the characteristics of simple and easy operation and convenient industrial production, and the obtained adsorbent can be used as N in the PSA/VPSA oxygen production process 2 And O 2 The selective adsorbent of (1).
Description
Technical Field
The invention relates to a preparation method and application of a molecular sieve adsorbent based on LiNaKLSX, belonging to the technical field of adsorbents.
Background
With the development of industry, the consumption of oxygen in various industries is increasing day by day, and the traditional cryogenic oxygen production method is gradually replaced by the pressure swing adsorption oxygen production process due to the defects of large energy consumption, long time for starting and stopping, inapplicability to small-scale oxygen production and the like. The LiLSX molecular sieve is used as a pressure swing adsorption air separation oxygen production adsorbent and has the advantages of large nitrogen adsorption capacity and high nitrogen-oxygen separation coefficient. The key of the pressure swing oxygen production technology is to prepare the efficient nitrogen-oxygen separation adsorbent. At present, the types of oxygen-making molecular sieves mainly include A type and X type, wherein a low silicon-aluminum ratio (LSX) molecular sieve with the Si/Al molar ratio of 1.0-1.1 has regular and uniform pore channels and is easy to exchange with larger cations. CN105984881A discloses a high-efficiency lithium-based oxygen generation molecular sieve and a preparation method thereof, CN105600803A discloses an LSX type zeolite molecular sieve synthesis process based on coal series kaolin synthesis, and CN102874837A directly synthesizes a low-silicon aluminum molecular sieve LSX from kaolin. CN101289197B the invention introduces a preparation method of low-silicon X-type molecular sieve raw powder LSX. The problem that the pure X-type molecular sieve with low silica-alumina ratio can be synthesized only by adding seed crystals exists in the preparation process
The adsorption performance of molecular sieves is generally closely related to the type and number of cations adsorbed. Therefore, the modified zeolite can be prepared through cation exchange, and the nitrogen adsorption performance of the molecular sieve is further improved. Particularly, the LiLSX molecular sieve after lithium exchange has higher N 2 The characteristics of good adsorption capacity, nitrogen-oxygen separation coefficient and oxygen enrichment performance become a hotspot of research. The technical method for preparing the LiLSX molecular sieve adsorbent conventionally is to exchange a NaLSX molecular sieve with Li +. Research shows that when the Li + exchange degree is lower than 70%, the molecular sieve is opposite to N 2 The adsorption capacity of (A) is hardly changed, and the molecular sieve pair N is only changed when the Li + exchange degree is increased from 70% to 100% 2 The adsorption capacity of (a) increases linearly. The LiLSX molecular sieve is prepared by methods such as an aqueous solution exchange method, a molten salt exchange method, steam exchange and the like. However, the conventional exchange method has the problems of low utilization rate of Li ions and large waste, and industrial production is restricted. Moreover, the demand of Li + for preparing the LiLSX molecular sieve is large, and with the rapid development of lithium ion batteries and the reduction of lithium reserves, the price of lithium has been increasing since 2016 years, resulting in a relatively high production cost of the LiLSX molecular sieve. CN101289196B introduces a preparation method of a LiLSX molecular sieve, LSX is subjected to K + exchange, then N h 4+ solution is used for multiple replacement, and then N h 4LSX is subjected to Li + exchange with LiO h solution. Patent CN 101766987A discloses a preparation method of a lithium-containing modified low-silicon aluminum X-type molecular sieve adsorbent, and provides a modification method in which two exchanges and two roasts are alternately carried out. Although the method can improve the Li + exchange degree and the stability of the molecular sieve framework, the method obviously complicates the whole modification process and increases the energy consumption, and the complicated process is obviously difficult to realize in large-scale industrial production.
In the field of PSA/VPSA air separation oxygen generation, a LiLSX molecular sieve is favored. The invention aims to synthesize and prepare a cheap molecular sieve adsorbent which can be used for gas separation. The pressure swing adsorption device is suitable for VSA, VPSA and PSA in various occasions, and can separate nitrogen and oxygen from air to prepare oxygen and oxygen-enriched air and prepare oxygen for medical treatment by a small oxygen preparation device. Has the characteristic of high nitrogen adsorption capacity.
Disclosure of Invention
The invention overcomes the defects of the prior art, and solves the technical problems that: provides a preparation method and application of a molecular sieve adsorbent based on LiNaKLSX, and synthesizes and prepares the molecular sieve adsorbent which can be used in the field of PSA/VPSA air separation oxygen generation and has higher oxygen production.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a LiNaKLSX molecular sieve adsorbent comprises the following steps:
the method comprises the following steps: preparing a lithium sodium potassium type low-silicon X type molecular sieve LiNaKLSX molecular sieve;
(1) Uniformly mixing one or two of spodumene and lepidolite, calcining at 800-850 ℃ for 2-5 hours, cooling to normal temperature, crushing, and sieving with a 100-200-mesh sieve for later use;
(2) Uniformly mixing sodium hydroxide, sodium metaaluminate and potassium hydroxide, adding deionized water, uniformly stirring, then adding the powder prepared in the step (1), heating to 80-90 ℃, stirring for 5-10 hours, cooling to room temperature, slowly adding water glass, stirring for 0.5-2 hours at 10-30 ℃, heating to 60-80 ℃, stirring for 3-6 hours, standing and aging for 16-48 hours, heating to 105-120 ℃, crystallizing at constant temperature for 5-15 hours, filtering after the reaction is finished, washing with water until the pH value of filter residue is 8-10, and then drying to prepare the LiNaKLSX molecular sieve;
step two: exchanging LiNaKLSX molecular sieve into a LiLSX molecular sieve through Li +, and controlling the percentage content range of lithium in the obtained LiLSX molecular sieve to be 5-9%;
adding a LiNaKLSX molecular sieve into deionized water which is 8-15 times of the LiNaKLSX molecular sieve, adding a lithium-containing solid under the condition of stirring, adding lithium according to the mass ratio of 1: 1-10, uniformly mixing, and exchanging for 3-5 times at 100-150 ℃, wherein the exchange time is 5-15 hours each time, and the molar ratio of the LiNaKLSX molecular sieve to the lithium refers to the mass ratio of the molecular sieve to the lithium ions in the lithium-containing solid; cleaning the exchanged sample with deionized water in an amount which is 3-5 times that of the sample, performing suction filtration, and drying at normal temperature to obtain LiLSX molecular sieve powder;
step three: mixing the prepared LiLSX molecular sieve powder with clay, adding an auxiliary agent according to the mass ratio of 80-95% of the total weight of the raw powder to 5-20% of the total weight of the clay, forming by a pelletizer or a strip extruding machine, drying at room temperature to 150 ℃, heating the dried product at the temperature rising speed of 10-20 ℃/min at the temperature of 250-350 ℃ for 3-6 hours, continuing to heat to 550-650 ℃, roasting for 2-5 hours, and naturally cooling to room temperature after finishing to obtain the adsorbent.
The LiNaKLSX molecular sieve is an X molecular sieve with the Si/Al molar ratio of 1.0-1.1.
And the lithium-containing solid in the second step is selected from one or more of lithium hydroxide, lithium chloride, lithium nitrate or lithium sulfate.
The lithium-containing solid in the second step is preferably lithium hydroxide, or lithium chloride, or a combination of lithium hydroxide and lithium chloride.
In the third step, the clay is one or more of halloysite, kaolin, attapulgite and pseudo-boehmite.
The auxiliary agent used in the third step is one or a mixture of deionized water and herba hyperici japonici solution; the addition amount of the auxiliary agent is 5-20% of the total mass of the molecular sieve powder and the clay calculated by mass ratio.
The maximum temperature of the roasting treatment in the third step is 550-650 ℃, and the roasting time is 2-5 hours.
Application of molecular sieve adsorbent based on LiNaKLSX as N in PSA/VPSA oxygen generation process 2 And O 2 The selective adsorbent of (1).
Compared with the prior art, the invention has the following beneficial effects:
1. the invention introduces the treated spodumene and/or lepidolite during the synthesis, reduces the addition amount in the Li exchange process, can effectively reduce the preparation cost, adopts dilute LiCl solution, does not need water washing during the filtration, thereby avoiding the loss of Li + caused by h + replacement of Li + due to hydrolysis;
2. the invention adopts a direct synthesis mode, avoids the problems of external seed crystal production and poor metering of the seed crystal, and is convenient for industrial production;
3. the invention adopts Li + to directly exchange Na + and K + in the LiNaKLSX molecular sieve, but not adopts the conventional process of firstly exchanging Na + by K + and then exchanging K + by N h 4+ and finally exchanging N h 4+ by Li +, and has the characteristics of simplicity, easy operation and convenient industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a preparation method of an adsorbent based on a LiNaKLSX molecular sieve, which comprises the following steps:
the method comprises the following steps: preparing a lithium sodium potassium type low-silicon X type molecular sieve LiNaKLSX molecular sieve;
(1) Uniformly mixing one or two of spodumene and lepidolite, calcining for 2-5 hours at 800-850 ℃, cooling to normal temperature, crushing, and sieving by a 100-200-mesh sieve for later use;
(2) Uniformly mixing sodium hydroxide, sodium metaaluminate and potassium hydroxide, adding a proper amount of deionized water, uniformly stirring, then adding the powder prepared in the step (1), heating to 80-90 ℃, stirring for 5-10 hours, cooling to room temperature, slowly adding water glass, stirring for 0.5-2 hours at 10-30 ℃, heating to 60-80 ℃, stirring for 3-6 hours, standing and aging for 16-48 hours, heating to 105-120 ℃, crystallizing at constant temperature for 5-15 hours, filtering after the reaction is finished, washing with water until the pH value of filter residue is 8-10, and then drying to obtain the LiNaKLSX molecular sieve;
step two: exchanging LiNaKLSX molecular sieve into a LiLSX molecular sieve through Li +, and controlling the percentage content range of lithium in the obtained LiLSX molecular sieve to be 5-9%;
adding a LiNaKLSX molecular sieve into deionized water which is 8-15 times of the LiNaKLSX molecular sieve, adding a lithium-containing solid under the condition of stirring, adding lithium according to the mass ratio of 1: 1-10, uniformly mixing, and exchanging for 3-5 times at 100-150 ℃, wherein the exchange time is 5-15 hours each time, and the molar ratio of the LiNaKLSX molecular sieve to the lithium refers to the mass ratio of the molecular sieve to the lithium ions in the lithium-containing solid; cleaning the exchanged sample with deionized water in an amount which is 3-5 times that of the sample, performing suction filtration, and drying at normal temperature to obtain LiLSX molecular sieve powder;
step three: mixing the prepared LiLSX molecular sieve powder with clay, adding an auxiliary agent according to the mass ratio of 80-95% of the total weight of the raw powder to 5-20% of the total weight of the clay, forming by a pelletizer or a strip extruding machine, drying at room temperature to 150 ℃, heating the dried product at the temperature rising speed of 10-20 ℃/min at the temperature of 250-350 ℃ for 3-6 hours, continuing to heat to 550-650 ℃, roasting for 2-5 hours, and naturally cooling to room temperature after finishing to obtain the adsorbent.
The LiNaKLSX molecular sieve is an X molecular sieve with the Si/Al molar ratio of 1.0-1.1.
And the lithium-containing solid in the second step is selected from one or more of lithium hydroxide, lithium chloride, lithium nitrate or lithium sulfate.
The lithium-containing solid in the second step is preferably lithium hydroxide, or lithium chloride, or a combination of lithium hydroxide and lithium chloride.
In the third step, the clay is one or more of halloysite, kaolin, attapulgite and pseudo-boehmite.
The auxiliary agent used in the third step is one or a mixture of deionized water and herba hyperici japonici solution; the addition amount of the auxiliary agent is 5-20% of the total mass of the molecular sieve powder and the clay according to the mass ratio.
The maximum temperature of the roasting treatment in the third step is 550-650 ℃, and the roasting time is 2-5 hours.
Application of LiNaKLSX molecular sieve adsorbent used as N in PSA/VPSA oxygen generation process 2 And O 2 The selective adsorbent of (1).
The following examples will enable one skilled in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
Example 1
Uniformly mixing 5000g of spodumene (containing Li2O 6%) and 3500g of lepidolite (containing Li2O 5%), calcining at 850 ℃ for 3 hours, cooling to normal temperature, crushing into powder by using a crusher, and sieving by using a 200-mesh sieve for later use;
uniformly mixing 1565g of sodium hydroxide, 3416ml of sodium metaaluminate and 863g of potassium hydroxide, adding 2000ml of deionized water, uniformly stirring, adding 200g of the powder prepared in the step (a), heating to 90 ℃, stirring for 5 hours, cooling to room temperature, slowly adding water glass, stirring for 3 hours at 10 ℃, heating to 60 ℃, stirring for 6 hours, standing and aging for 48 hours, heating to 120 ℃, crystallizing at constant temperature for 5 hours, after the reaction is finished, filtering, washing with water until the pH value of filter residue is 8, and drying to prepare the LiNaKLSX molecular sieve; 25 ℃,50% relative humidity, saturated water absorption 30.6%, crystallinity 91%, composition Si/Al =1.01.
Example 2
1565g of sodium hydroxide, 3416ml of sodium metaaluminate and 863g of potassium hydroxide are uniformly mixed, 2000ml of deionized water is added, 200g of the powder prepared in the step (a) is added after uniform stirring, the mixture is heated to 80 ℃ and stirred for 10 hours, the mixture is cooled to room temperature, water glass is slowly added, the mixture is stirred for 0.5 hour at 30 ℃, the mixture is heated to 80 ℃ and stirred for 3 hours, then the mixture is kept stand and aged for 16 hours, the mixture is heated to 105 ℃ and crystallized at constant temperature for 15 hours, after the reaction is finished, the mixture is filtered, washed with water until the pH value of filter residue is 10, and then the mixture is dried to prepare the LiNaKLSX molecular sieve; 25 ℃,50% relative humidity, saturated water absorption 31.5%, crystallinity 93%, composition Si/Al =1.02.
Example 3
Weighing 500g of LiNaKLSX molecular sieve prepared according to the embodiment 1, adding the LiNaKLSX molecular sieve into 4000g of deionized water, then adding 810g of lithium hydroxide solid under the stirring condition, uniformly mixing, exchanging for 15 hours at 100 ℃, filtering the exchanged sample, washing with 1500g of deionized water, performing suction filtration, drying at normal temperature, and repeating the process for 3 times to prepare the LiLSX molecular sieve. The obtained LiLSX molecular sieve is detected by an inductively coupled plasma emission spectrometer (ICP-OES), and the detection result shows that the percentage content of lithium oxide is 5.4%.
Example 4
Weighing 800g of LiNaKLSX molecular sieve prepared according to the embodiment 2, adding the LiNaKLSX molecular sieve into 12000g of deionized water, then adding 11200g of lithium chloride solid under the stirring condition, uniformly mixing, exchanging for 5 hours at 150 ℃, filtering the exchanged sample, washing with 4000g of deionized water, performing suction filtration, drying at normal temperature, and repeating the process for 5 times to prepare the LiLSX molecular sieve. The obtained LiLSX molecular sieve is detected by an inductively coupled plasma emission spectrometer (ICP-OES), and the detection result shows that the percentage content of the lithium oxide is 8.7%.
Example 5
Weighing 500g of the LiLSX molecular sieve powder prepared according to the embodiment 4, mixing with 20g of halloysite, 30g of kaolin and 5g of attapulgite, adding 80g of deionized water and 10g of sesbania powder solution, forming by a ball forming machine, drying at 150 ℃, heating the dried product at the temperature rising speed of 20 ℃/min and the temperature of 350 ℃ for 3 hours, continuing to heat to 650 ℃, roasting for 2 hours, and naturally cooling to room temperature after finishing to obtain the adsorbent. The adsorption capacity of nitrogen was 0.99mmol/g as measured at room temperature under 0.1 MPa.
Example 6
Weighing 500g of the LiLSX molecular sieve powder prepared according to the embodiment 4, mixing with 35g of kaolin and 25g of attapulgite, adding 100g of deionized water, molding by a strip extruding machine, drying at room temperature, heating the dried product at a heating rate of 10 ℃/min at a temperature of 250 ℃ for 6 hours, continuously heating to 550 ℃, roasting for 5 hours, and naturally cooling to room temperature after finishing to obtain the adsorbent. The adsorption capacity of nitrogen gas was measured at room temperature under 0.1MPa to be 1.03mmol/g.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of a molecular sieve adsorbent based on LiNaKLSX is characterized by comprising the following steps:
the method comprises the following steps: preparing a lithium sodium potassium type low-silicon X type molecular sieve LiNaKLSX molecular sieve;
(1) Uniformly mixing one or two of spodumene and lepidolite, calcining at 800-850 ℃ for 2-5 hours, cooling to normal temperature, crushing, and sieving with a 100-200-mesh sieve for later use;
(2) Uniformly mixing sodium hydroxide, sodium metaaluminate and potassium hydroxide, adding deionized water, uniformly stirring, then adding the powder prepared in the step (1), heating to 80-90 ℃, stirring for 5-10 hours, cooling to room temperature, slowly adding water glass, stirring for 0.5-2 hours at 10-30 ℃, heating to 60-80 ℃, stirring for 3-6 hours, standing and aging for 16-48 hours, heating to 105-120 ℃, crystallizing at constant temperature for 5-15 hours, filtering after the reaction is finished, washing with water until the pH value of filter residue is 8-10, and then drying to prepare the LiNaKLSX molecular sieve;
step two: passing LiNaKLSX molecular sieves through Li + Exchanging into a LiLSX molecular sieve, and controlling the percentage content range of lithium in the obtained LiLSX molecular sieve to be 5-9%;
adding a LiNaKLSX molecular sieve into deionized water which is 8-15 times of the LiNaKLSX molecular sieve, adding a lithium-containing solid under the condition of stirring, adding lithium according to the mass ratio of 1: 1-10, uniformly mixing, and exchanging for 3-5 times at 100-150 ℃, wherein the exchange time is 5-15 hours each time, and the mass ratio of the LiNaKLSX molecular sieve to the lithium refers to the mass ratio of the molecular sieve to the lithium ions in the lithium-containing solid; cleaning the exchanged sample with deionized water in an amount which is 3-5 times that of the sample, performing suction filtration, and drying at normal temperature to obtain LiLSX molecular sieve powder;
step three: mixing the prepared LiLSX molecular sieve powder with clay, adding an auxiliary agent according to the mass ratio of 80-95% of the total weight of the raw powder to 5-20% of the total weight of the clay, forming by a pelletizer or a strip extruding machine, drying at room temperature to 150 ℃, heating the dried product at the temperature rising speed of 10-20 ℃/min at the temperature of 250-350 ℃ for 3-6 hours, continuing to heat to 550-650 ℃, roasting for 2-5 hours, and naturally cooling to room temperature after finishing to obtain the adsorbent.
2. The method for preparing the LiNaKLSX molecular sieve adsorbent according to claim 1, which is characterized in that: the LiNaKLSX molecular sieve is an X molecular sieve with the Si/Al molar ratio of 1.0-1.1.
3. The method for preparing the LiNaKLSX molecular sieve adsorbent according to claim 1, which is characterized in that: and the lithium-containing solid in the second step is selected from one or more of lithium hydroxide, lithium chloride, lithium nitrate or lithium sulfate.
4. The method for preparing LiNaKLSX molecular sieve adsorbent according to claim 3, which is characterized in that: and the lithium-containing solid in the second step is lithium hydroxide, or lithium chloride, or the combination of the lithium hydroxide and the lithium chloride.
5. The method for preparing the LiNaKLSX molecular sieve adsorbent according to claim 1, which is characterized in that: in the third step, the clay is one or more of halloysite, kaolin, attapulgite and pseudo-boehmite.
6. The method for preparing the LiNaKLSX molecular sieve adsorbent according to claim 1, which is characterized in that: the auxiliary agent used in the third step is one or a mixture of deionized water and herba hyperici japonici solution; the addition amount of the auxiliary agent is 5-20% of the total mass of the molecular sieve powder and the clay according to the mass ratio.
7. The method for preparing the LiNaKLSX molecular sieve adsorbent according to claim 1, which is characterized in that: the maximum temperature of the roasting treatment in the third step is 550-650 ℃, and the roasting time is 2-5 hours.
8. The application of the molecular sieve adsorbent prepared based on the preparation method of the LiNaKLSX molecular sieve adsorbent according to claim 1 is characterized in that: the LiNaKLSX molecular sieve adsorbent is used in a PSA/VPSA oxygen production process as N 2 And O 2 The selective adsorbent of (1).
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